Hybrid HF–DFT modeling of monolayer water adsorption on (001) surface of cubic BaHfO3 and BaZrO3 crystals

First-principles calculations have been used to study the atomic structure, preferred sites and adsorption energies for water adsorption at different terminations of the cubic phase of perovskite-structured BaHfO3 and BaZrO3. By considering different initial positions of water molecules, the possibility of water dissociation has been investigated. It is demonstrated that the site selectivity and the form of adsorbed molecule can be affected by the choice of surface unit cell. Dissociative adsorption was found to be favorable for all surfaces in consideration. Hydroxylation of ZrO2- and HfO2-terminated surfaces is accomplished by a noticeable reconstruction of the surface structure of cubic phase towards the orthorhombic phase. Calculated atomic charges in bare and hydroxylated surfaces show that BaHfO3 crystal is slightly more ionic than BaZrO3.